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Preparation method for polyvinyl alcohol/attapulgite-polyion liquid catalytic esterification composite membrane

A technology of polyionic liquid and polymeric ionic liquid, which is applied in the field of membrane materials, can solve the problems of being easily corroded by alcohol, reducing the swelling of the membrane to oil and methanol, and being easily damaged, and achieves the effect of low price and reduced material cost

Active Publication Date: 2015-11-18
HUAIYIN TEACHERS COLLEGE
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The existing problems are: (1) crosslinking or heat treatment will make the film brittle and reduce the hydrophilicity. In the production of biodiesel, the increase of the degree of crosslinking will reduce the swelling of the film to oil and methanol, and the oil and methanol will The diffusion rate to the surface and interior of the catalytic membrane will be reduced, resulting in a decrease in the yield of biodiesel; (2) The single polymer matrix membrane lacks chemical and thermal stability, and it is easily damaged in an alcohol environment for a long time; (3) Esterification The functional groups on the reaction graft are easily corroded and detached by alcohol during the reaction process
Traditional carrier and immobilization methods have solved the problem of ionic liquid recovery to a certain extent. However, heterogeneous reactions (three phases of triglyceride, alcohol and solid catalyst) make the catalytic efficiency of ionic liquids low (problem 4), And it is easily corroded and peeled off by alcohol during application (consistent with the above problem (3))
Such as Liang et al. [Green Chemistry, 2010, 12:201-204.] Synthesized a kind containing 4 SO 3 The acidic ionic liquid of H group, because it contains multiple functional groups, this ionic liquid shows extremely high acidity and polarity, and the highest yield of biodiesel reaches 98.3%. When the water increases from 0.3% to 2.0%, its The yield only dropped from 98.3% to 95.3%, showing good water resistance, and biodiesel products meet the EN14214 standard. Unfortunately, this ionic liquid has no functional groups for chemical bonding and immobilization, and the synthesis cost is high

Method used

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  • Preparation method for polyvinyl alcohol/attapulgite-polyion liquid catalytic esterification composite membrane
  • Preparation method for polyvinyl alcohol/attapulgite-polyion liquid catalytic esterification composite membrane
  • Preparation method for polyvinyl alcohol/attapulgite-polyion liquid catalytic esterification composite membrane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Add 1 g of attapulgite-polymeric ionic liquid catalyst (ATP-PILs) to 99 mL of distilled water, stir at room temperature for 2 h to prepare a 1 wt.% ATP-PILs1 suspension; put 5 g of PVA into a beaker filled with 95 mL of deionized water, and use Stir the glass rod for 10 minutes, seal it, stir at 80°C for 2.5 hours, then cool to room temperature, vacuum defoam for 4 hours, and make a 7wt.% PVA solution; each take 25mL of ATP-PILs1 suspension and PVA solution and mix them at 1:1, seal , stirring at room temperature for 2 hours at 1200r / min, ultrasonic degassing for 30 minutes, vacuum degassing for 4 hours, and standing for 24 hours to obtain the casting solution; scrape the casting solution on a smooth and clean glass plate to form a wet film of a certain thickness, and then Dry at room temperature in an ultra-clean bench for 24 hours, then peel off the dry film from the glass plate and sandwich it between two glass plates covered with non-woven fabrics, place...

Embodiment 2

[0028] Example 2: The difference from Example 1 is that ATP-PILs1 is selected as the model catalyst, and 100g of ATP-PILs1 suspension with a mass fraction of 1wt.%-10wt.% is configured. Other preparation and analysis methods are the same as in Example 1. The prepared composite membrane catalyzes The performance is as follows:

[0029] Mass fraction of ATP-PILs1 suspension 1% 5% 10% final conversion rate 58.5% 90.1% 91.8% The final conversion rate after repeating 4 times 51.5% 87.6% 85.8%

Embodiment 3

[0030] Example 3: Take 5g of ATP-PILs1 and add it to 95mL of distilled water, stir at room temperature for 2h to prepare a 5wt.% ATP-PILs1 suspension; put PVA into a beaker filled with deionized water, stir with a glass rod for 10 minutes, and seal it with a glass rod at 80°C Stir at constant temperature for 2.5 hours, then cool to room temperature, vacuum defoam for 4 hours, and make 100g of 5wt.%-10wt.% PVA solution; each take 25mL of ATP-PILs1 suspension and PVA solution and mix at 1:1, seal, and stir at room temperature at 1200r / min After 2 hours, ultrasonic degassing for 30 minutes, and then vacuum degassing for 4 hours, then let it stand for 24 hours to obtain the casting solution; scrape the casting solution on a smooth and clean glass plate to form a wet film of a certain thickness, and then place it in the ultra-clean bench at room temperature Dry for 24 hours, then remove the dry film from the glass plate and sandwich it between two glass plates covered with non-wov...

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Abstract

The invention discloses a preparation method for a polyvinyl alcohol / attapulgite-polyion liquid catalytic esterification composite membrane. The preparation method comprises the following steps: adding an attapulgite clay / polyion liquid composite catalyst (ATP-PILs) immobilized with a high-density acidic site into a polyvinyl alcohol (PVA) solution for alloying to form a membrane casting solution, and stewing for defoaming; then coating a smooth and clean glass plate or a microhole basement membrane with the defoamed membrane casting solution; then performing drying, heating and crosslinking after-treatment to form a per-vaporized compact catalytic esterification membrane with a catalysis function. The PVA dense membrane is filled with attapulgite immobilized with the high-density acidic site, so that the mechanical strength and the thermal and chemical stability of the membrane are improved; furthermore, the surface of the catalysis membrane has the high-density acidic catalysis site, and an efficient integrated membrane reaction-separator is constructed; in the catalytic esterification reaction of oleic acid and methyl alcohol, the oleic acid methyl alcohol conversion rate is up to about 90 percent; after the polyvinyl alcohol / attapulgite-polyion liquid catalytic esterification composite membrane is repeatedly used for 4 times, the oleic acid methyl alcohol conversion rate is reduced by about 5 percent or less.

Description

technical field [0001] The invention belongs to the technical field of membrane materials, and in particular relates to a preparation method of a hybrid membrane used for catalytic esterification-pervaporation separation "integrated coupled" membrane reactor. Background technique [0002] Biodiesel is a long-chain fatty acid methyl ester produced by transesterification of animal and vegetable oils and methanol. It is a high-quality substitute for petroleum diesel. At present, its main industrial preparation method is the transesterification process, and most of the catalysts use strong acid and strong alkali. There are problems such as serious equipment corrosion, complicated subsequent separation procedures, and large amounts of industrial wastewater and waste residues. [0003] In recent years, the "integrated coupled" membrane reactor for catalytic esterification-pervaporation separation is considered to be a potential breakthrough technology in the field of biodiesel, an...

Claims

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Application Information

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IPC IPC(8): B01D71/38B01D71/42B01D71/68B01D69/12B01D69/02B01D67/00
Inventor 李梅生赵宜江周守勇张文王杰薛爱莲吴飞跃
Owner HUAIYIN TEACHERS COLLEGE
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